JP4762885B2 - Electrochromic particles - Google Patents

Description

Detailed Description of the Invention

  The present invention relates to electrochromic particles. In particular, the present invention relates to electrochromic particles suitable for use in electrochromic devices.

  Electrochromic devices comprising electrodes based on nanostructured conductive or semiconductive films with surface adsorbed electrochromic compounds are known, inter alia, from WO-A-98 / 35267 and WO-A-01 / 27690. It has been. Such electrodes are prepared by applying a nanostructured conductive or semiconductive film to a conductive substrate, annealing at high temperature, and then chemisorbing the electrochromic compound onto the surface of the nanoparticles in the film. This is a time consuming technique and limits the electrode substrate material to high temperature resistant materials such as glass or ceramic. It would be desirable to provide conductive, semiconductive or insulating nanoparticles having an electrochromic compound adsorbed on their surface prior to application to a substrate, thereby avoiding the disadvantages of the prior art.

  In accordance with the present invention, there are provided separate electrochromic particles comprising conductive, semiconductive or insulating nanoparticles having one or more electrochromic compounds adsorbed on the surface.

  The present invention also provides methods for preparing the electrochromic particles of the present invention, electrodes comprising the particles, and their use in the manufacture of electrodes for electrochromic devices. The electrodes of the present invention can be rigid or flexible depending on the choice of substrate material.

  As used herein, the term “electrochromic compound” or “(electro) chromophore” is intended to refer to a compound that changes color when a potential is applied, but excludes polymers and inorganic compounds.

  As used herein, the term “nanoparticle” is intended to refer to discrete and dispersible particles having an average particle size of up to 80 nm, preferably up to 50 nm, and more preferably up to 30 nm.

  As used herein, the term “conductive nanoparticle” is intended to refer to a nanoparticle having no electronic band gap; the term “semiconductive nanoparticle” refers to a band gap of 5 electron volts or less. And the term “insulating nanoparticles” is intended to refer to nanoparticles having a band gap greater than 5 electron volts.

  The electrochromic particles of the present invention may exist in the form of a solid or may be suspended in a solvent.

  The electrochromic compound (or compounds) preferably adsorbs to the surface of the nanoparticles so that there is up to 100% of the nanoparticles and at least 1% of the monolayer coated nanoparticles are present.

Conductive or semiconductive nanoparticles are preferred. Preferred nanoparticles are those of the following metals: titanium, zirconium, hafnium, chromium, molybdenum, indium, tin, tungsten, vanadium, niobium, tantalum, silver, zinc, cerium, strontium, iron (divalent and trivalent) or nickel Selected from doped or undoped oxides or their perovsky, preferably TiO ₂ , WO ₃ , SnO ₂ , MoO ₃ , In ₂ O ₃ / SnO ₃ or ZnO. Preferred dopants include F, Cl, Sb, P, As, B, Al, In, Ga, Si, Sn, Ti, Ge, Zr, Li and Hf.

  Insulating nanoparticles that can be used in the present invention include oxides of silicon, aluminum, zirconium, barium, magnesium and sodium.

  The electrochromic compounds adsorbed on the surface of the nanoparticles may be the same or different and may conveniently be n-type or p-type. Preferred electrochromic compounds for use in the present invention are WO-A-98 / 35267, WO-A-01 / 27690, WO-A-03 / 001288 and Applicant under the name “Electrochromic Compounds” ( In a pending international application filed on the same day by NTera Limited). Particularly preferred n-type compounds include bis- (2-phosphonoethyl) -4,4′-bipyridinium dichloride, 1-phosphonoethyl-1 ′-(2,4,6-trimethylphenyl) -4,4′-bipyridinium dichloride. Bisimide and 1-phosphonoethyl-1 ′-(4-styryl) -4,4′-bipyridinium diperchlorate are included.

Particularly preferred p-type compounds are:
β- (10-phenothiazyl) propoxyphosphonic acid;
β- (10-phenothiazyl) propyl-phosphonic acid;
β- (10-phenothiazyl) propionate phosphonic acid;
β- (10-phenoxazyl) propionate phosphonic acid; and (1-ferrocenyl) imido-benzylmethylphosphonic acid.

  The electrochromic compounds used in the present invention may also contain reactive groups that can be activated to form chemical bonds between adjacent electrochromic compounds on the same particle or on adjacent electrochromic particles. Hereinafter, it is referred to as a crosslinking group in the present specification. These groups are conveniently located on the electrochromic molecule at the opposite end of the surface binding group. Alternatively, the bridging group can be attached to the nanoparticle, for example via an alkyl group, and the alkyl group can be linked to a binding group on the nanoparticle surface. Since each particle can contain a large number of these reactive groups on its outer surface, activation of these groups leads to three-dimensional crosslinking of the particles. Activation can be initiated by thermal, ionic, reductive, oxidative, radical, photochemical or electrochemical means. Suitable reactive groups include vinyl, styryl, (meth) acrylate, epoxy, silane, amine, alcohol, carboxylic acid and carboxylic acid halide. In certain cases, activation can occur by reaction with additional chemical groups such as bridging molecules such as dicarboxylic acids, diamines or dialcohols.

The following table demonstrates this:

  The bridging group is bonded to the chromophore group via a bond illustrated by a bold line. This bridging group can be activated through different schemes, but some of such schemes require the addition of an initiator (ie, A2, A4, A6, A7, A8) that will be included in the printing formulation. Some require only heat or light as an initiator. A preferred scheme includes an activation process step after printing. This allows better control when the printed film can be cross-linked. Accordingly, preferred methods include exposure to heat, light, or electrochemical potential (A1, A3 and A5) that may or may not be facilitated by the presence of additional chemical initiators in the formulation and film.

  Crosslinking of the electrochromic particles increases the mechanical strength of the resulting film. Crosslinking eliminates the need for a polymer binder and makes electrochromic particles particularly suitable for ink jet printing.

  The electrochromic particles of the present invention may further comprise one or more compounds on the surface of the nanoparticles that interfere with or inhibit aggregation of electrochromic compounds adsorbed on the nanoparticles. Suitable aggregation inhibiting compounds include alkane phosphonates and cationic pyridiniums carrying one or more anchor functional groups such as phosphonoethylpyridinium perchlorate.

  The electrochromic particles of the present invention are obtained by mixing conductive, semiconductive or insulating nanoparticles and one or more electrochromic compounds in a solvent and, if desired, isolating the resulting electrochromic particles. Can be prepared.

  The nanoparticles can be suspended in the solvent prior to mixing with the electrochromic compound (or compounds) in the solvent. In the latter case, the nanoparticle solvent and the electrochromic compound solvent are preferably the same. Mixing is typically performed at a temperature of approximately 25 ° C. for approximately 30 minutes to 2 hours. The resulting electrochromic particles can be isolated, for example, by centrifugation and any suitable means such as drying at a temperature in the range of approximately 50 ° C. to 90 ° C. for approximately 6 hours to 30 hours.

  Suitable solvents for suspending the nanoparticles and electrochromic compound and dispersing the dried electrochromic particles include diethyl ether, 1,1,1-trichloroethane, amyl acetate, carbon tetrachloride, xylene, ethyl acetate. , Toluene, tetrahydrofuran, N-methylpyrrolidone, benzene, chloroform, trichloroethylene, methyl ethyl ketone, acetone, diacetone alcohol, ethylene dichloride, methylene chloride, pyridine, morpholine, dimethylformamide, dimethyl sulfoxide, methanol, ethanol, n-propanol N-butanol, propylene glycol, ethylene glycol, glycerin and water. Preferred solvents include ethanol, N-methylpyrrolidone and water.

  To form the electrode, the dried electrochromic particles can be dispersed to form a paste in a solvent such as N-methylpyrrolidone or polyvinyl difluoride, such as stencil coating or ink jet printing or screen printing. Can be applied to a suitable substrate. The paste on the substrate can be dried at a temperature in the range of about 50 ° C to 200 ° C, preferably about 80 ° C to 150 ° C. The substrate may be formed, for example, from glass, ceramic, metal or plastic, which may optionally be coated with a layer of conductive material such as tin oxide doped with fluorine or antimony.

  If the one or more electrochromic compounds present on the electrochromic particles contain one or more crosslinking groups, a crosslinking initiator may be added to the dried dispersion of electrochromic particles.

  An electrochromic device can be formed by providing a counter electrode, sealing the counter electrode to an electrode containing the electrochromic particles of the present invention, and then incorporating an ionically conductive medium.

The electrochromic particles of the present invention have the following advantages:
1. It can be deposited on the electrode in a single process step at a relatively low temperature, thereby allowing the use of heat sensitive materials such as plastic, such as a flexible substrate for the electrode;
2. It allows greater control of the final image pixel size and resolution, especially when small pixel sizes and more than one colored pixel are required on the same electrode or image;
3. The color of the electrochromic particles can be controlled by changing the nature and relative amount of the chromophore. For example, (i) electrochromic particles having different chromophores can be mixed uniformly, the resulting film will display the corresponding mixed color, and (ii) different electrochromic particles having different chromophores. Deposit side by side on the substrate, thereby offering the possibility of increasing the amount of information on the display. Such pixels consisting of electrochromic particles can be individually addressed to achieve a high resolution multicolor display device.

The invention is illustrated in the following examples.
Example 1
The electrochromic particles consist of 0.1 M bis- (2-phosphonoethyl) -4,4′-bipyridinium dichloride (1.118 g) and 0.01 M lithium perchlorate (0.0266 g) as chromophore in 25 ml water. It was prepared by dissolving. 5 g TiO ₂ powder (30 nm average particle size) was added to the chromophore solution. The mixture was stirred at 25 ° C. for 1 hour and then centrifuged at 5000 rpm to separate the electrochromic particles. Electrochromic particles were redispersed in ethanol to dissolve any non-chemisorbed chromophore molecules and separated again from the rinse solution by centrifugation at 5000 rpm. Thereafter, the washed solid was dried at 70 ° C. for 24 hours.

To prepare the cathode, 4 g of dried electrochromic particles were dispersed in 6 g of N-methylpyrrolidone to form a paste. This paste was stencil-coated on a fluorine-doped tin oxide (FTO) glass substrate and the substrate was dried using the following thermal cycle immediately after printing the paste:
From room temperature (25 ° C.) to approximately 100 ° C. for 15 minutes;
30 minutes at 100 ° C;
Cool to room temperature (25 ° C.) over 30 minutes.

  The resulting cathode was then rinsed in ethanol to remove any chemisorbed chromophore molecules.

Example 2
Electrochromic particles were prepared by dissolving 500 mg of mesidine bisimide (ie, 1-phosphonoethyl-1 ′-(2,4,6-trimethylphenyl) -4,4′-bipyridinium dibisimide) in 100 ml of methanol. Was added over 20 minutes to 200 ml of methanol containing 2.5 g of suspended TiO ₂ nanoparticles. Mesidine-bisimide is an electrochromic compound disclosed and claimed in a co-pending European patent application entitled “Electrochromic Compounds” filed on the same day by the present applicant (NTera Limited). When the addition was complete, the mixture was stirred for 1 hour at 25 ° C. and then centrifuged at 5000 rpm to separate the electrochromic particles. The electrochromic particles were redispersed in ethanol to dissolve any non-chemisorbed chromophore molecules and separated again from the rinse solution by centrifugation at 5000 rpm. Thereafter, the washed solid was dried at 70 ° C. for 24 hours.

To prepare the cathode, 4 g of dried electrochromic particles were dispersed in 6 g of N-methylpyrrolidone to form a paste. This paste was stencil-coated on a fluorine-doped tin oxide (FTO) glass substrate and the substrate was dried using the following thermal cycle immediately after printing the paste:
From room temperature (25 ° C.) to 60 ° C. for 15 minutes;
30 minutes at 60 ° C;
Cool to room temperature (25 ° C.) over 30 minutes.

  The resulting cathode was then rinsed in ethanol to remove any chemisorbed chromophore molecules.

Example 3
The electrochromic particles consisted of 500 mg 1-phosphonoethyl-1 ′-(4-styryl) -4,4′-bipyridinium diperchlorate, 200 ml methanol containing 2.5 g suspended TiO ₂ nanoparticles. It was prepared by dissolving. 1-phosphonoethyl-1 ′-(4-styryl) -4,4′-bipyridinium diperchlorate is disclosed in WO-A-03 / 001288. The mixture was allowed to stir at 25 ° C. for 1 hour, after which it was centrifuged at 5000 rpm to separate the electrochromic particles. The electrochromic particles were redispersed in ethanol to dissolve any non-chemisorbed chromophore molecules and separated again from the rinse solution by centrifugation at 5000 rpm. Thereafter, the washed solid was dried at 70 ° C. for 24 hours.

  To prepare the cathode, 4 g of dried electrochromic particles are dispersed in 6 g of N-methylpyrrolidone containing 300 mg of azobisisobutyronitrile (AIBN) as a photoinitiator to form a printing paste. did. The paste was stencil-coated on an indium oxide-tin oxide (ITO) glass substrate. Immediately after coating, the substrate was dried and the film was crosslinked at 80 ° C. for 60 minutes.

Example 4
The cathode (40 mm × 40 mm) was prepared according to the procedure of Example 1.
In order to prepare a counter electrode, a glass substrate (50 mm × 50 mm) coated with fluorine-doped tin oxide (FTO) as a transparent conductive oxide was coated with antimony-doped tin oxide (ATO) by screen printing, and 60 ° C. For 20-30 minutes. A white reflective paste containing rutile titania white pigment particles was coated on the ATO layer by screen printing and the bilayer was sintered at 450 ° C. for 45 minutes.

  The cathode was sealed to the counter electrode using an epoxy gasket seal. The resulting electrochromic device was backfilled with 0.2 M electrolyte solution of lithium perchlorate in gamma-butyrolactone under vacuum and cured under UV light. Application of 1.3 V across the electrochromic device results in device color development.

FIG. 1 shows the UV-visible light reflection spectrum of the electrochromic particles prepared in Example 1; FIG. 2 is a cyclic voltammogram of the electrochromic device of Example 4 at a scan rate of 10 mV / sec. The starting voltage for device color development is approximately -0.8 volts, which is very advantageous from the standpoint of device energy consumption; FIG. 3 shows the chronocoulometry behavior (charge vs. time) of the device when a pulse of −1.3 volts is applied to the device of Example 4. The amount of charge corresponding to complete color development is approximately 4 mC / cm ² . Combined with a low onset voltage, this charge consumption results in low power consumption for devices containing these films; and FIG. 4 shows a white state (short circuit indicated by a solid line) and a coloring state (immediately after applying a coloring voltage (−1.3 V) pulse indicated by a chain line), and at the same time after 15 minutes held in an open circuit. Fig. 4 shows the reflectivity of the device of Example 4 (illustrated by the dashed line ----). A reflectance as high as 45.62% is obtained in the white state and a reflectance as low as 7.74% is obtained in the colored state, which gives a contrast ratio of 5.89. These results compare very well with those obtained using devices of the type disclosed in WO-A-98 / 35267 and WO-A-01 / 27690.

Claims (33)

Conductive with electrochromic compounds in excess or equal to 1 were adsorbed on the surface, seen including a semi-conductive or insulating nanoparticles, the nanoparticles have an average particle size of up to 80 nm, electrochromic particles separated from each other.   The electrochromic particles of claim 1 present in the form of a solid or suspension.   The electrochromic particle according to claim 1 or 2, wherein the nanoparticle has an average particle size of up to 50 nm. The electrochromic particle of claim 3, wherein the nanoparticle has an average particle size of up to 30 nm. The electrochromic particle according to any one of claims 1 to 4 , wherein the nanoparticle is conductive or semiconductive. The nanoparticles are doped with the following metals: titanium, zirconium, hafnium, chromium, molybdenum, indium, tin, tungsten, vanadium, niobium, tantalum, silver, zinc, cerium, strontium, iron (divalent and trivalent) or nickel The electrochromic particle according to any one of claims 1 to 5, wherein the electrochromic particle is selected from an undoped oxide or a perovsk of the metal . The nanoparticles are TiO ₂ , WO _Three , SnO ₂ , MoO _Three , In ₂ O _Three / SnO _Three Or the electrochromic particle of Claim 6 which is ZnO. Electrochromic according to claim 6 or 7 , wherein the metal oxide is doped with F, Cl, Sb, P, As, B, Al, In, Ga, Si, Sn, Ti, Ge, Zr, Li and Hf. particle. The electrochromic particle according to any one of claims 1 to 8, wherein the electrochromic compound is of n-type or p-type.   The electrochromic compound is of the n-type and comprises bis- (2-phosphonoethyl) -4,4′-bipyridinium dichloride and 1-phosphonoethyl-1 ′-(4-styryl) -4,4′-bipyridinium 10. Electrochromic particles according to claim 9, selected from chlorates. The electrochromic compound is of the p-type and is β- (10-phenothiazyl) propoxyphosphonic acid; β- (10-phenothiazyl) propyl-phosphonic acid; β- (10-phenothiazyl) propionate phosphonic acid; 10. Electrochromic particles according to claim 9, selected from-(10-phenoxazyl) propionate phosphonic acid; and (1-ferrocenyl) imido-benzylmethylphosphonic acid. The electrochromic particle according to any one of claims 1 to 11, wherein the electrochromic compound or each electrochromic compound contains one or more crosslinking groups. The electrochromic particle according to claim 12 , wherein the crosslinking group is selected from vinyl, styryl, (meth) acrylate, epoxy, silane, amine, alcohol, carboxylic acid and carboxylic acid halide. The electrochromic particle according to any one of claims 1 to 13 , wherein the nanoparticle further comprises one or more compounds on its surface that prevent or inhibit aggregation of the electrochromic compound adsorbed to the nanoparticle. 15. Electrochromic particles according to claim 14 , wherein the compound that inhibits aggregation is selected from alkanephosphonates and cationic pyridiniums carrying one or more anchor functional groups. A method for preparing separated electrochromic particles comprising conductive, semiconductive or insulating nanoparticles having one or more electrochromic compounds adsorbed on a surface comprising:
Providing conductive, semiconductive or insulating nanoparticles with an average particle size of up to 80 nm,
The nanoparticles are mixed with one or electrochromic compound in a solvent beyond that, if desired, the resulting electrochromic including methods that Mick particles isolated. The method of claim 16, wherein the nanoparticles have an average particle size of up to 50 nm. The method of claim 17, wherein the nanoparticles have an average particle size of up to 30 nm. 19. A method according to any one of claims 16 to 18 wherein the nanoparticles are isolated and mixed in the solvent prior to mixing with one or more electrochromic compounds in the solvent. 20. The method of claim 19 , wherein the solvent used to suspend the nanoparticles and the solvent for dissolving one or more electrochromic compounds are the same. The method according to any one of claims 16 to 20 , wherein the solvent is ethanol, N-methylpyrrolidone or water. The method according to any one of claims 16 to 21 , further comprising drying the isolated electrochromic particles. A method for manufacturing an electrode or an electrochromic device, comprising:
The electrochromic particles separated from each other according to any one of claims 1 to 15 are dispersed in a solvent so as to form a paste, and the paste is applied to a substrate so as to form a first electrode. Including methods. The method of claim 23 , further comprising drying the paste on a substrate at a temperature in the range of 50 ° C to 200 ° C. The method of claim 24 , further comprising drying the paste on a substrate at a temperature in the range of 80 ° C to 150 ° C. 26. A method according to any one of claims 23 to 25 , wherein the paste is applied by stencil coating or ink jet printing or screen printing.   27. A method according to any one of claims 23 to 26, wherein the substrate is formed from glass, ceramic, metal or plastic. 28. The method of claim 27, wherein the substrate is coated with a layer of conductive material. 29. The method of claim 28, wherein the layer of conductive material comprises tin oxide doped with fluorine or antimony. Electrochromic 1 or a bridging group beyond that one or electrochromic compound exceeds that of the electrochromic particles include A method according to any one of claims 23 to 29 including a crosslinking initiator in the paste. 31. The method of any one of claims 23 to 30 , further comprising preparing a counter electrode to form an electrochromic device, sealing the counter electrode to the first electrode, and incorporating an ionically conductive medium. The method described. An electrode or electrochromic device comprising the electrochromic particles according to any one of claims 1 to 15 . Use of the electrochromic particles according to any one of claims 1 to 15 in the manufacture of electrodes or electrochromic devices.

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